Azo dyes from hydroxy-naphtho-diazine derivatives



Patented Mar. 1% 1 929.

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WILHELME HEEZBERG", OF BERLIN- WILMEESDORF, AND HEINRICH; OHLENDORF, OF BERLIN-FRIEDENAU, GERMANY, ASSIG'NGRS, BY MESINE ASSIGNMENTS, T0 GEL-AS SELLI DYESTUFF GORPOEATIGN, OF NEW YGRK, N. Y., A CORPORATION OF DELA- WARE.

A DYE FROM EYDRQXY-NAPHTHO-DIAZINE DERIVATIVES.

l lo Drawing. Application filed. oetober 4, 1926, Serial No. 139,548, and in Germany June 9, 1925.

In German specification 394,195 there are described para-diazine derivatives which are obtained by alkaline fusion of para-diazine derivatives containing sulpho groups. The sulpho groups by this process successively are replaced by hydroxyl groups, the hydroxyl group in the 8-position of the conjugated naphthalene ring in the alkaline melt giving rise to a condensation reaction.

The present invention relates to new azo dyes derived from a diazo compound and a hydroxy-para-diazinederivative being a substitution product of a compound probably of the general formula:

B being an aromatic-radicle, this diazine oxide resulting by alkaline fusion of a substitution product of a compound probably corresponding to the general formula:

The new dyes are destroyed by strong reducing agents.

By treating only a small quantity of the dyes with a cold so ution of stannous chloride in strong hydrochloric acid a bluish solution is formed, the coloration of which changing to yellowish brown after some time, especially on heating.

The following examples are given in order to illustrate the invention Without limiting it the parts being by Weight:

Example 1.The diazo compound from. 173 parts of 1-aminobenzenei-sulphonic acid is allowed to flow into a solution in 6000 parts of Water and d0 parts of sodium hydroxide of 260 parts of the product probably correspondmg to the formula:

NI) l n SOaH or 4- hydroxy 8 sulf0-1.2-naphtho phenazine:

SOaH

The 4.8-disulfo-l-naphtho-phenazine mentioned may be prepared from 1.2-naphthoquinone-4-.8-disulfonic acid and 1.2-diaminobenzene; the 4-hydroXy-8-sulfo-LQ-naphthophenazine is obtainable from d-hydroxy-LQ- naphthoquinone-8-sulfonic acid and 1.2-diamino-benzine. There are then added 110 parts of anhydrous sodium carbonate. the course of several hours the coupling is complete. The dyestufl is salted out and Worked up as usual. When dry it is a dark brown powder. On wool the dyestufl yields yellow tints of good fastness to fulling and excellent fastness to light.

The corresponding dyestuff from l-aminonaphthalene-tsulphonie acid dyes animal fibres red with a yellowish sheen. l-aminoazo-benzene-F-sulphonic acid yields a dyestufi which dyes animal and vegetable fibres red. If diazo compounds are used which are derived from aminoazo-dyestufi's, dyes are obtained which, dye cotton in general red brown to blackish brown shades.

salt of the diazine compound used in Example 1 is coupled with the diazo compound from 4-amino-1-methylbenzene-3-sulphonic acid. The dye forms with metal salts lakes which are insoluble in Water. The loarium-,

calciumand particularly the copper lakes yield in painting or printing brown tints of excellent fastness to light and of good covering power.

By use of other suitable diazosulphonic .acids even a deeper brown may be obtained.

Example 3.Thediazo compound from 22.4 parts of 2-amino-4l-chloro-1-hydroxybenzene-5-sulphonic acid is added to a solution of 26.2 parts of the diazine compound used in Example 1 in the equivalent proportion of sodium hydroxide solution and in the course of several hours a solution of 8 parts of sodium hydroxide in 50 parts of Water is added drop by drop. When coupling is complete the dye may be salted out. It dyes WOOl orange brown. By after-chroming or dyeing in the presence of a chromium mordant a violet brown tint is obtained. The dyeings have excellent fastness to Washing, fulling and sulphur and good fastness to steaming.

The dye probably corresponds to the formula:

I N/O t N II N OaNa The dye, Worked up in the usual manner, dyes wool fast red.

The corresponding dye from diazotized Ewample 2.The solution of the sodium l-aminobenzeneA-sulphonic acid dyes animal fibre fast orange.

Example 5.-The diazo compound from l-sulphonic acid are diazotized and coupled with 230 parts of sodium-1amino-naphthalene-G-sulphonate, dissolved in 2500 parts of Water with addition of 100 parts of crystal lized sodium acetate. After further dia7otizing the product is coupled under the cohditions given'in Example 5 with the diazinecompound prescribed in Example 4. The dye dyes cotton red brown. It probably corresponds to the formula:

sosNa By coupling the hydroxydiazine compound used in the Example 4: With the equivalent proportion of 4-chloro-2-diazo-l-hydroxybenzene-5-sulphonie acid or by ananalogons ortho-hydroxydiazo compound there are obtained mordant dyes of the character of that made in accordance with Example 3.

Eamnple '7.The diazine compound prescribed in Example 4 is coupled in alkaline solutionwith the equivalent proportion of 2-diazonaphthalene-l-sulplionic acid. The dye yields insoluble barium salts and calcium salts Which are Bordeaux-red pigments suitable for oil paints and carpet printing. The excellent covering power and surprising fastness to light of these compounds are remarkable.

In a similar manner other hydroxy-paradiazine compounds of the mentioned general constitution may be used. F or instance, the compound of the probable formula:

obtainable by alkaline fusion of 3.S- lisul[o- LQ-naphtho-phenazine yields with diazoarylsulphonie acids fast brown to violet brown wool dyes. The compound obtainable by alkaline fusion of 6.8-disulpho-1.2.1.2- dinaphthazine or 6.8-disulpho-1.2.2.1-di- V naphthazine and probably corresponding to the formula respectively gives by combining with diazobenzene sulphonic acids and also by combining with diazonaphthalene sulphonic acids dyes dyeing wool orange to violet brown.

WVhat we claim is, 1. As new products, the azo dyestuffs of the formula:

ANI'Q' I in which R, stands for a radicle off the group including the benzene and naphthalene series substituted by at least onesulfonic acid group R for a radicle of the group including the benzene and naphthalene series, and one X stands for an hydroxyl group and the other X for hydrogen, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to washing and to light.

3. As new products, the azo dyestufis of the 'formula:

HO N

in which R, stands for a radicle of the group including the benzene and naphthalene series substituted by at least one sulfonic acid group, and R stands for a radicle of the group including the benzene and naphthalene series, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to washing and to light.

4. As new products, the azo dyestuffs of the formula N \NI) t in which R, stands for a radicle of the group including the benzene and naphthalene series substituted 'by at least one sulfonic acid group, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent tastness to washing and to light.

5. As new products, the azo. dyestuffs of the formula:

wherein one Y stands for a substituent of the group including chloro and nitro and the other Ys represent hydrogen, R stands for a radicle of the group including the ben- Zeno and naphthalene series, and the naphthalene nucleus A is substituted by at least one hydroxyl group, which dye animal and vegetable fibers generally yellow to brown to violet shades of excellent fastness to washing and to light.

6. As new products, the azo dyestuffs of the formula:

on 0 Y y g 1 H038 Y W I Y l -v l wherein one Y stands for a substituentof the group including chloro and nitro and the other Ys represent hydrogen, R stands for a radicle of the group including the henzene and naphthalene series, and one X stands for an hydroxyl group and the other X for hydrogen, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to washing and to li ht.

7. As new products, the azo dyestuffs of the formula:

the formula Y N=N- HOaS Y wherein one Y stands for a substituent of the group including chloro' and nitro and the other Ys represent hydrogen, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to washing and to light.

9. As new products, the azo dyestuffs of the formula:

in which R stands for a residue of the group including the benzene and naphthalene series, and the naphthalene nucleus A is substituted by at least one hydroxyl group, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to washing and to light.

I 10. As new products, the azo dyestuffs of the formula:

in which R stands for a residue of the group including the benzene and naphthalene series, and one X'stands for an hydroxyl group and the other X for hydrogen, which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to Washing and to light.

11. As new products, the azo dyestuffs of the formula:

in which R, stands for a radicle of the group including the benzene and naphthalene series and which dye animal and vegetable fibres generally yellow to brown to violet shades of excellent fastness to washing and to light.

12.; As a new product, the azc dyestufi of the formula-z. i v a OH -HO 15. Materials dyed with the dyestu'fi's of claim 3.

16. Materials dyed with the dyestuffs of claim 4.

17. Materials dyed with the dyestuffs claim 5.' 18'. Materials dy'edwith the dyestuffs claim 6. v

' 19.' Materials dyed with the dyestuffs claim 7. y Y 20. Materials dyed with the dyestuffs claim 8. 21. Materials dyed with the dyestuffs claim 9.

22. Materials dyed with the dyestuffs claim 10.

23. Materials dyed with the dyestufl's claim 11.

24. Materials dyed with the dyestuffs claim 12. 40

In testimony whereof we'afiix our signa- I tures.

WILHELM HERZBERG. HEINRICH OHLENDORF. 

